Hydrazino-1,3,5-triazino derivatives of substituted phenylarsenic compounds



' As atom in the molecule of Patented Dec. 11, 1945 UNITED STATES.PATENT OFFICE DERIVATIVES OESUBSSTITUTED PHENYLARSENIC COM- POUND ErnstA. H. Friedheim, New York, N. Y, No Drawing. Application February 3',1942,

Serial No. 429,4

4 Claims.

I w z-c o"NHNH-A wherein A is a radical selected from a group which inmy present application is denoted as "group I. This group consists of H,

(CsHz-D,E-AsOsH2) -(C6H2 D,EAS=X) and and is so meant in the claims. Inthese formulas radicals D and E are selected from a group, which in mypresent application is denoted as group II. This group consists of H,halogen, OH, O-alkyl, alkyl, alkylol, N02, NHz, NH-alkyl, N-dialkyl,NH-acyl, NH-NH2, NH-NHacyl, N- acyl- NI-Iz, N-acylNH-=acyl,N-alkyl-NI-h, N- alkylNH-alkyl, alkylaminamino-CO--NH2 and is so meantin the claims; X is a divalent radical selected from the groupconsisting of O, S, dihalides, sulfur containing groups of the type=(SR) 2, R being a radical capable of carrying a SH-radical; X is anarsenic radical comprisinga trivalent As atom, two valencies of whichare connected to As, while its remaining monovalent bond is connected toan atom group which is identical with the entire rest of the molecule towhich the monovalent bond of the the condensation product is connected.When in the above general formula A is hydrogen, the radicals Y and Zmay be the same or difierent. One of the radicals Y and Z is selectedfrom the group denoted in my present application as group III. Thisgroup i in the claims.

When in the above general formula A is a radical of the formula-(CsH2'D,E-ASQ3H2), -(CeHaD,E-As=X), and -(C6H2--D,E- As=X'), theradicals Y and Z may be the same or different, and are selected from theradicals NH-C6I-I2-D,EAsO3Hz, -NH-NHCeHz- D,EAsO3I-I2,NI-I-CeHz-D,E-As=X, and NHNHCeI-IaD,E-As=X, or from the above describedgroup IV. r

I have found that organic arsenicals pertaining to the present inventionmay be prepared according to the following methods:

(a) A 1,3,5-triazine derivative containing at least one halogen isreacted with a phenylhydrazino-arsonic acid according to the equation:

(b) A 1,3,5-triazine derivative containing at least one hydrazine group,and one halogen reacts with an anilino-arsonic acid as follows:

IVE-N112 \N (c) A 1,3,5-triazine derivative containing at least onehydrazino group may be reacted with a halogen-phenyl-arsonic acidaccording to the equation:

I Z-() JNHNH-C@HzD,E-AsOaH2 HCl (d) A halogen-triazinyl-arsonic aciddescribed in my co-pending application Ser. No. 310,232

filed Dec. 20, 1939, and containing at least one 422,234, filed Dec. 9,

with S02 in hydrochloric acid solution in the presence of hydriodic acidas catalyst.

' (1) By treating the As -containing products according to thisinvention with hypophosphorous acid (HsPOz) or stannous chloride inhydrochloric acid solution in the presence of hydriodic acid ascatalyst, or by treating the same with sodium hydrosulfite (NazS2O4) inneutral or alkaline solution, the corresponding trivalentarseno-compounds, 1. e. compounds containing the group --As- As-, areformed.

The equations described above under (a), (b) and (c) are given asexamples for purpose of illustration.

When in the above equation Y and/or Z represent halogen, one or bothhalogens may be substituted, after formation of the condensationproduct, in one or two steps by one radical or two different radicalsselected from the group consisting of -NH-CsH2-D,E-ASO3H2,

group IV. I have further found that those condensation productsaccording to this invention, which contain at least one freehydrazino-radical (-NH-NHz) compounds carrying a carand from reactreadily with bonyl group said carbonyl group being capable of reactingwith phenylhydrazine to form hydrazones; and with aceto-acetic-esters toform pyrazolones.

The condensation products according to this invention representvaluable, active therapeutic agents in diseases caused by spirochaetesand protozoae, such as syphilis, and African sleeping sickness. V

A particular feature of the present invention resides in the fact thatit opens large fields of protein and carbohydrate chemistry toarsenicchemo therapy. Arsenic compounds according to this invention maybe combined, by exchange of triazine-halogen, with such importantphysiological substances, as amino-acids, polypeptides, proteins,guanidine, guanine, adenine, thiamine (vitamin B1). Furthermore, byhydrazone-linkage, arsenic-containing compounds embodying the presentinvention may be condensed with essential physiological compounds, suchas glucose, lactose, vitamin C (ascorbic acid), vitamin'Bz (riboflavin)and vitamin K.

The above mentioned formation of pyrazolone derivatives leads not onlyto new arsenic-containing derivatives of this pharmacologicallyimportant compound, but paves the way for new arsenic-containingdyestuffs, as pyrazolone derivatives combine readily with aromaticdiazoniu-m compounds to form azo-dyes.

Example I.- grams of sodium nitrate dissolved in 300 cc. of water arerun, with stirring and cooling, into an ice cold solution obtained bydissolving 217 gr. of arsanilic acid in 250 cc. of hydrochloric acid(spec. gr. 1.19) and 1000 'cc. of water. The reaction mixture is runslowly, with stirring and cooling into a solution prepared by dissolving1400 gr. of NezSzOrand 336 gr. of sodium'acetate in 6000 cc. of water. Awhite crystalline precipitate sonic acid is formed, which is filteredoff, washed with aqueous 10% acetic acid, and redissolved in dilutehydrochloric acid. After boneblacking of the acid solution, it isreprecipitated by addition of sodium acetate, separated by filtrationand washed with aqueous 10% acetic acid, alcohol and ether. The compoundis soluble in alkali carbonate solutions and in dilute mineral acids. Itreduces ammoniacal silver solution. It is insoluble in benzol and etherand dissolves without color in concentrated sulfuric acid.

11.6 gr. of pure p-hydrazino-phenyl-arsonic acid are suspended in 250cm. of water containing 8.8 gr. of sodium bicarbonate, and shaken, at 2C. with a solution of 9.1 gr. of cyanuric chloride in 100 cc. ofchloroform until a sample of the chloroform proves to be free ofcyanuric chloride. The chloroform is now separated from the aqueoussuspension. The latter is acidified with hydrochloric acid withCongo-red as an indicator. A white precipitate is formed which isseparated by filtration and washed with water, alcohol and ether. Theprecipitate is suspended in 10 times its weight of water and broughtinto solution, except for a small insoluble residue, by adding sodiumbicarbonate up to a slightly alkaline reaction to litmus. The solutionshowing a slight yellow tint, is boneblacked and liltered. Onacidification of the colorless filtrate with sulfuric acid [(2,4)-dichloro-1,3,5-triazinyl- (6) l-p-hydazino-phenyl-arsonic acidprecipitates. It is filtered off and Washed with water, alcohol andether. a

The compound is soluble in dilute aqueous solutions of sodiumbicarbonate, sodium carbonate and ammonia. It precipitates from itsalkaline of p-hydrazino-phenylarsolution on careful acidification withmineral acids. It is soluble in an excess of dilute hydrochloric acid.

It is insoluble in ethanol, acetone, chloroform and other. It forms acolorless solution in conce'ntrated sulfuric acid, whichtakes a deepredviolet color on addition of solid sodium nitrate.

ltdissolves in 30% nitric acidwith a reddishbrown color. It reducesammoniacal silver ni tratesolution.

Stannous chloride added to the solution of the compound in hothydrochloric acid produces in the presence of hydriodic acid, a yellow,flocculent precipitate.

Example II.- l part of [(2,4)-dichloro-l,3,5- ltriazinyl- ('6) lhydrazino phenyl arsonic acid corresponding to Example I, is dissolvedin 30' parts of a 10% aqueous hydrazine hydrate solution at atemperature of 30 C. On acidification with acetic acid,[(2,4)-chloro-hydrazino-1,3,5- triazinyl- (6) l-hydrazino-phenyl-arsonicacid is formed as white precipitate, which is filtered off and washedwith aqueous acetic acid and recrystallized out of dilut hydrochloricacid. The compound is soluble in aqueous sodium bicarbonate solution andin an excess of dilute mineral acids, insoluble in acetone and ether. Itreduces ammoniacal silver solution, and gives with a hot solution ofsilver nitrate in nitric acid a shaking, the substance dissolves whilethe solution becomes hot and takes a yellow color. After 24 hours, thesolution is poured into 50 parts of ethyl alcohol. The hydrazine salt of[(2,4)- dihydrazino -l,3,5triazinyl -(6) p hydrazinephenyl-arsonic acidprecipitates in form of a yellowish viscous paste which is separated bydelcantation and washed with ethyl alcohol until all excess of hydrazinehydrate is removed. It is then triturated with 6 parts of dilutedsulfuric acid of 20%. The resulting suspension of hydrazine sulfate ischilled and filtered. On careful neutralization of the acid filtratewith aqueous ammonia, free [(2,4-dihydrazino-1,3,5-triazinyl-(6)]'-p-hydrazino-phenylarsonic acid is formed as a whitemicro-crystalline precipitate which is separated 'byfiltration andwashed with water, ethyl alcohol and ether.

The compound is soluble in aqueous solutions -1 sodium bicarbonate,sodium carbonate and ammonia and in dilute mineral acids.

It is only slightly soluble in cold and hot water, insoluble in alcohol,acetone and ether.

It forms a colorless solution in concentrated sulfuric acid which takesa deep red to redviol'et color on addition of solid sodiuni mtrate.

It reduces in the cold Fehling's solution and a solution of silvernitrate in aqueous ammonia.

Thehydroohloric acid solution of the compound produces a yellowprecipitate with cinnamic aldehyde and a reddish brown precipitate with1,2- .naphthoquinon'e.

The compound reacts in boiling dilute acetic acid with ethyl acetoaceticester to form a pyrazolone which couples readily with aromaticdiazocompounds.

Stannous chloride added to the solution of the compound in-hothydrochloric acid produces, in

the presence of hydriodic acid, a-yellow flocculent precipitate. l 1

Example IV.-A suspension of one mol of til hydrazino-triazine in a 5%suspension of the disodium salt of one mol of p-bromo-benzenearsonicacid in mcnochlor benzene is shaken with one gram of copper powder(copper bronze Natur Kupfer C. Ullmann) for 24 hours at 100 C.

After cooling, the reaction mixture is filtered.

The residue is extracted with an aqueous bicarbonate solution. Thealkaline solution thus obtained is acidified with hydrochloric acid andfiltered.

The acid filtrate yields on exact neutralization with ammonia, a. whiteprecipitate of [(2,4) dihydrazino- 1,3,5 -triazinyl- (6)-p-hydrazino-phenylarsonic acid which is identical with the compoundproduced according to Example III.

Example V.- -1 part of [(2,4)-dichloro-l,3,5- triazinyl (6) phydrazino-phenylarsonic acid corresponding to Example I is dissolved inparts of 15% aqueous ammonia,- at a temperature of 30 C. Onacidification with acetic acid, [(2,4) chloro-amino 4,3,5 triazinyl(6)]p ydrazino-phenylarsonic acid is formed as a white precipitate, whichis filtered off, Washed with dilute acetic acid and recrystallized outof dilute aqueous hydrochloric acid. The compound is soluble in aqueousalkali and an excess of dilute mineral acid. It dissolves without colorin con centrated sulfuric acid. It is insoluble in chloroform.

Example VI.-One part of [(2,4) -dichloro-- 1,3,5.-triazinyl -(6)p-hydrazino phenylarsonic acid according to Example I is suspended at C.in 20 parts of liquid ammonia. At con-'- stant volume, the temperatureis allowed to rise slowly to 25 C. The residue remaining afterevaporation of the ammonia, is taken up with 20 parts of water. Theaqueous solution is filtered and yields on acidification with aceticacid a White precipitate of [(2,4) -diamino-l,3,5-triazinyl -(6)'] phydrazine phenylarsonic acid, which is filtered and recrystallized outof dilute hydrochloric acid.

The compound is soluble in aqueous bicarbon ate and in an excess ofdilute mineral acid, insoluble in hexane and ether.

I he same compound is obtained by treating [(2,4)-chloroamino-1,3,5-triazinyL-(6)] phydrazino-phenylarsonic acid,described in Example V, with hot concentrated ammonia.

Example VII.-One part of [(2,4 chloroanfino-'1,3,5-triazinyl-(6)lp-hydraZino-pheny-L arsonic acid, described in Example V is treated witha aqueous solution of hydrazine hydrate in a procedure in all wayssimilar to that described in Example III.

Afterelimination of the excess hydrazine. as described in Example In,[(2-,4)'- amino-hydrazinc-1,3,5-triazinyl (6)] phydrazi-no-phenylarsonic acid is precipitated from a hydrochloric acidsolution, by neutralization with ammonia.

The compound forms a whit powder, is soluble in aqueous alkali anddilute mineral acids, insoluble in alcohol and ether.

In dilutehydrochloric acid solution it forms a white precipitate onaddition of benzaldehyde:

Example VlIL-el part of [(2,4) -dichloro-l,3,5= triazinyl-(G)l-p-amino-phenylarsonic acid described in my co-pending patentapplication Serial No. 310,232 filed December 20, 1939, is dissolved in30 parts of icecold 20% aqueous solution of hydrazine hydrate. Thesolution is allowed to stand for 8 hours at 25 C. The hydrazine salt of[(2,4) -chloro-hydrazino-1,3,5-triazinyl-(6)l-p-amino-phenylarsonic acidis pre cipitated by pouring the boneblacked and filtered solution in anexcess of ethanol. The precipitate is filtered oil, washed with alcoholand brought into solution with 10 times its weight of water on additionof sodium bicarbonate. The slightly alkaline solution is boneblacked andfiltered. On acidification with acetic acid the free [(2,4)-chloro-hydrazino-1,3,5-triazinyl-(6)l p-aminophenylarsonic acid forms awhite micro-crystalline precipitate which is filtered off and washedwith dilute acetic acid, alcohol and ether. The compound is soluble indilute aqueous bicarbonate and an excess of dilute, warm hydrochloricacid. It is insoluble in acetone, chloroform and ether. It reduces warmammoniacal silver nitrate solution. The warm hydrochloric acid solutionreacts with cinnamic aldehyde to form a yellow precipitate.

The same compound is obtained by shaking an 8% solution of 1 mol ofarsanilic acid and 2 mols of sodium bicarbonate at C. with 1 mol offinely divided 2,4-dichloro-6-hydrazino-1,3,5- triazine obtained bytreating an ice cold ether solution of cyanuric chloride with oneequivalent of hydrazine dissolved in ether.

Example IX.3.5 gr. of hydrazine dissolved in I 50 cc. of etherare addedwith stirring and coolture is vigorously shaken while the temperature isallowed to rise to 33 C., while the ether is permitted to escape. Whenall primary amine has disappeared, the reaction mixture is adjusted to areaction alkaline to lithmus, charcoaled and filtered. On acidificationof the filtrate with acetic acid, [(2,4)-chloro-hydrazino-1,3,5-triazinyl-(6)l-p-aminophenylarsonic acid forms awhite precipitate, which is filtered Off WaShBd with dilute acid,alcohol and ether and recrystallized out of warm dilute hydrochloricacid. The compound is identical with the compound obtained according toExample VIII.

Example X.l part of [(2,4)-chlorohydrazino-1,3,5-triaziny1-(6)lp-amino-phenylarsonic acid prepared as described Examples VIII and IX,is treated on the water bath, in a pressure bottle for 2 hours with 2.5parts of 75% aqueous solution of hydrazine hydrate. The compound goesinto solution. On cooling, the hydrazine salt of [(2,4)-dihydrazino-1,3,5-triazinyl- (6) p-aminophenylarsonic acid forms awhite crystalline precipitate which is filtered oil and washed withalcohol and ether.

1 part of this compound is dissolved in 4 parts of warm water. Thesolution is boneblacked and filtered. On addition of 1 part of anhydroussodium acetate, the free [(2,4)-dihydrazino-l,3,5- triazinyl (6) lp-amino phenyl arsonic acid forms a white crystalline precipitate, whichis filtered oil and washed with alcohol and ether. The compound issoluble in dilute aqueous alkali, such as solutions of sodiumbicarbonate, carbonate, hydroxide and ammonia.

From the concentrated alkaline solution it is \precipitated by aceticacid, dilute hydrochloric,

or sulfuric acid. It is soluble in an excess 01 dilute hydrochloricacid. It is insoluble in hol, acetone and chloroform. a

It reduces ammoniacal silver nitrate solution.

The'solution of thGCOl'IlIPOllIld in warm hydrochloric acid reacts withcinnamic aldehyde to form a yellow precipitate.

In hydrochloric acid solution it forms, on addition of stannouschloride, in the presence of hydroiodio acid a fiocculent, yellowprecipitate.

The above described compound may also be obtained by replacing bothhalogens of [(2,4)- dichloro 1,3,5 triazinyl-(6) l-p-aminophenylarsonicacid in one step by the hydrazino radical. This can be efiected bytreating said dichlorocompound with a warm concentrated solution ofhydrazine-hydrate.

Example XI.1 part of [(2,4)-chloro-hydrazino- 1,3,5-triaz1'nyl-(6)l-p-amino-phenylarsonic acid is treated under pressure, at 50 C. with 20parts of liquid ammonia.

The residue remaining after the opening and airing of the pressurevessel is dissolved in 10 times its weight of water. The solution isboneblacked and filtered. On acidification with acetic acid, [(2,4)amino hydrazino-l,3,5-triaziny1-(6)l-p-amino-phenylarsorfic acid forms awhite precipitate which is filtered off and washed with dilute aceticacid, alcohol and ether.

The compound is soluble in aqueous sodium bicarbonate solution and in anexcess of dilute hydrochloric acid.

It reduces ammoniacal silver nitrate solution.

Dissolved in warm, dilute hydrochloric acid, it forms a whiteprecipitate with benzaldehyde.

Dissolved in warm, dilute hydrochloric acid, it forms a yellowflocculent precipitate on addition of hypophosphoric acid in presence ofhydroiodic acid.

Example XII.l part of [(2,4) -dihydrazino-1,3,5-triazinyl-(6)l-p-hydrazino phenylarsonic acid described in ExampleIII is dissolved in 50 parts of hydrochloric acid (spec. grav. 1.19)containing 1% of hydroiodic acid. The solution is treated :at 70 C. witha current of S02 gas. .On cooling, a white crystalline precipitate,representing the chlorhydrate of [(2,4) dihydrazino- 1,3,5-triazinyl-(6) l-p-hydrazino phenyldichlorarsine is formed which is filtered offand washed with ice-cold hydrochloric acid.

The precipitate is dissolved in 50 times its weight of airfreewater. Oncareful neutralization with aqueous ammonia, [(2,4) -dihydrazino-1,3,5-triazinyl-(6) l-p-hydrazino phenyl arsinoxide forms a whiteprecipitate which is filtered off and washed with air-free ice water.The compound is soluble in dilute hydrochloric acid, insoluble in diluteaqueous bicarbonate of soda, chloroform and benzene.

It dissolves without color in concentrated sulfuric acid. This solutionturns to a red-violet tint on addition of sodium nitrate. It reducesFehlingssolution and ammoniacal silver nitrate.

Example XIII .--el part of [(2,4) -diamino- 1,3,5- triazinyl-(6)l phydrazlno-phenylarsonic acid described in Example VI is dissolved in 10parts of 10% hydrochloric acid. To the solution are added 5 parts byweight of a solution prepared alcoarates as a yellow powder which isfiltered ofi and washed with methanol.

The product is soluble with yellow color in an excess of dilute warmhydrochloric acid. It is reprecipitated unchanged on neutralization ofthe acid solution by ammonia. The arseno compound thus preparedhas theformula:

ethanol. .A white. precipitate forms which isseparated bycentrifugingwashed with alcohol, dried and redissolved in 7 times its,weight of water, to

which sufficient carbonate. of soda isadded to make the reactionslightly alcaline to litmus. The solution is boneblacked and filtered. nacidification with acetic acid, [(2,4) -chloro-hydrazino-1,3,5triazinyl-(6) l-(3-4 amino-oxyphenylarsonic acid forms a whiteprecipitate which is filtered ofi and washed with ice water, alcohol andether.

The same compound may be obtained by shakingan 8% solution of3,4-amino-oxy-phenylarsenic acid and 1 /2 mol of sodium carbonate at 25C. with 1 mol of 'finely divided 2,4-dichloro-6-hydrazino-1,3,5-triazine by a procedure in all ways analogous to the onedescribed in Example Ix The resulting compound gives all reactions shownby [(2,4) -chloro-hydrazino-1,3,5-triazinyl- (6)l-p-aminophenyl-arsonicacid described in Examples VIII and IX, and, furthermore, its

alcaline solution develops a red color on addition ofdiazobenzenesulfonic acid.

Example XV.-1 part of [(2,4) -chloro-hydrazino-1,3,5-triazinyl-( 6)]-(3-4') -amino-oxyphenylarsonic acid obtained as described in ExampleXIV is suspended in IO parts of liquid ammonia at 40 C. At constantvolume the temperature is brought slowly to 35 C. and is maintained atthis level for 8 hours. The residue obtained after blowing off theexcess ammoniais dissolved in water. The solution is boneblacked andfiltered.

Onacidification with acetic acid [(2,4)-aminohydrazino-1,3,5 -triaziny1-(6 l- (3 ,4) -aminooxyphenylarsonic acid forms a white precipitate whichis filtered off, washed with water, alcohol and ether.

The compound is soluble in aqueous bicarbonate solution and dilutemineral acids, insoluble in acetone, choloroform and ether. It dissolveswithout color in concentrated sulfuric acid.

It reduces ammoniacal silver nitrate solution and couples in alcalinesolution with diazobenzene j sulfonic acid to give a red color.

azinyl-(B) l (324") -aminooxy-phenylarsonic acid is obtained 'bytreating [(2,4) -chloro hydrazinol,3,5-triazinyl-( 6) l (3-4') aminooxyphenylarsonic acid, obtained as described in Example XIV, withconcentrated aqueous hydrazine-hydrate solution by a procedure in allways analoous to that described in Examples III and VIII.

The compound shows all the properties described as typical for [(2,4)-dihydrazino-1,3,5- triazinyl-( 6) l-p-amino-phenylarsonic acid.Furthermore, it couples in alcaline solution with thediazobenzene-sulfonic acid to give a red color.

Example XVII .-3,4 hydrazino oxy phenylarsonic acid is prepared byreduction of 3,4-diazo-oxyphenylarsonic acid according to the methoddescribed in Example I. The compound is brought to reaction withcyanuric chloride by a procedure in all ways analogousto that describedin Example I, to form [(2,4) -dichloro-1,3,5-tri azinyl-( 6)l-3'-hydrazino-4 oxy phenylarsonic acid. This compound gives all thereactions indicated for the dichloro compound corresponding to ExampleI, and, furthermore, it couples in alcaline solution withdiazobenzene-sulfonic acid to form a red azo-dye.

Example XVIII.-1 part of [(2,4)-amino-hydrazino-1,3,5-triazinyl-( 6)l-(3-4) -amino oxyphenylarsom'c acid according to Example XV dissolvedin 40 parts of concentrated hydrochloric acid (spec. grav. 1.19)containing 1% of hydroiodic acid, is treated at 60 C. with a current-ofS02. On cooling, the dichlorhydrate of [(2,4)- amino-hydrazino-1,3,5triazinyl (6)] (3'.4') amino-oxy-phenyldichlorarsine forms a whitecrystalline precipitate.

The compound is soluble in methanol, insoluble in carbontetrachloride.It reduces ammoniacal silver nitrate. Treated with a dilute airfreesolution of alcali, it hydrolizes to the corresponding arsinoxyde.

ether. The compound of the formula IF'H-NHr HeN-ITTH o o As=As issoluble in caustic soda and in an excess of dilute hydrochloric acid. Itis insoluble in alcohol and benzene.

Example XX.1 mol of sodium-p-amido-benzene-sulfonate in a 7% aqueoussolution is added to a 5% solution of 1 mol of [(2,4) -dichloro1,3,5-triazinyl- (6) -3-hydrazino-4 -oxy-phenylarsonic acid containing 1 molof sodium carbonate. The reaction mixture is allowed to stand at roomtemperature until all aromatic amine has disappeared. The reactionmixture is filtered Ofi. On acidification of the filtrate withhydrochloric acid, a white precipitate is formed which is filtered ofiand washed with dilute hydrochloric acid and water. The moist compoundis treated under pressure at C. with 20 times the quantity of 30%ammonia. After theexcess of ammonia has been driven off, the reactionmixture is acidified with hydrochloric acid whereupon EZ-amino-A-sulfanilino-1,3,5 triazinyl-(6) ]-3'-hydrazino 4- oxy-phenyla-rsom'cacid of the formula:

, N AS03112 forms a white precipitate,

The compound is recrystallized out of warm water. It is soluble inaqueous bicarbonate and in an excess of dilute hydrochloric acid,insoluble V in acetone and ether. Its alcaline solution gives a redcolor with diazobenzene sulfonic acid.

Example XXI.A 2% solution of 1 mol of [2- amino-l-sulfanilino 1,3,5triazinyl-(fi) l-3'-hydraZinol'--oxi -phenylarsonic acid, obtained asdescribed in Example XX, in warm 5% hydrochloric acid is run understirring into a solution of 8 mols of stannous chloride in hydrochloricacid (spec. grav. 1.19)' containing of hydroiodic acid. On standing, ayellow precipitate is formed, which is filtered off, washed with colddilute hydrochloric acid, dissolved in dilute sodium hydrate andreprecipitated by acidification with hydrochloric acid. The compound ofthe for- The compound is soluble with yellow color in an aqueoussolution of carbonate of soda and slightly soluble in an excess ofdilute hydrochloric acid. It is insoluble in acetone and ether.

Example XXIII.1.3 parts of aceto-aceticethyl ester is added to asolution of 3.4 parts of [(2,4) amino hydrazino 1,3,5 triazinyl (6) lamino-phenyl arsonic acid corresponding to E xample XI, suspended in 100parts of 50% glacial acetic acid. The reaction mixture is stirred on thewater bath for 2 hours. On cooling the condensation product of theformula:

CHa-C(3Hl N\ oo N I i l NHr-C C--NHCaH4.ASO3H2 forms a whitemicro-crystalline precipitate con sisting of[2-amino-4-(methyl-pyrazolone) -1,3,5- triazinyl-(G)l-amino-phenylarsonic acid.

The compound is soluble in carbonate of soda, insoluble in acetone andether, In alcaline solution it couples with diazobenzene sulfonicacidand forms a yellow dye;

It is to be understood that in the appended claims the term aminoradicals is used to include -NI-I2 radicals as well as the bovedisclosed substituted amino radicals.

I claim: 7 1. A 1,3,5-triazine derivative of the formula wherein Yand Zare selected from the group consisting of amino, and hydrazino radicals,Cs represents a benzene ring, andD and E are selected from the groupconsisting of H, halogen, OH, -O-acy1, O-alkyl, amino and alkylradicals, said process comprising the step of reacting a 1,3,5-triazinederivative of the formula with a substituted phenylarsonic acid compoundcorresponding to the formula wherein one of T and W is a halogen radicaland the other is a.-NHNHz radical.

3. A process for the preparation of a 1,3,5-triazine derivative of theformula wherein Y and Z are selected from the group consisting of amino,and hydrazino radicals, Cs represents a benzene ring, and D and E areselected from the group consisting of H, halogen, 0H, -Oacy1. Oalky1,amino and alkyl radicals,

said process comprising the step of reacting a cyanuric halide of theformula llialogen t N N with a phenyl-hydrazino-arsonic acid compoundcorresponding to the formula and treating the reaction product formedwith a substance selected from the group consisting of ammonia,substituted amines and hydrazine hydrate.

4. A process for the preparation of a 1,3,5-triazine derivative of theformula I halogen-C wherein Y and Z are selected from the groupconsisting of amino, and hydrazino radicals, Cc represents a benzenering, D and E are selected from the group consisting of H, halogen, OH,-O-acy1, O-alky1, amino and alkyl radicals, said process comprisingsubjecting a hydrazinotriazino-derivative of a substituted phenylarsonic acid compound corresponding to the formula N II to the action ofS02 in hydrochloric acid solution in the presence of hydriodic acid.

ERNST A. H. FRIEHDHEIM.

